EP4655360A1 - Hotmelt adhesive - Google Patents

Abstract

Compositions, particularly pressure sensitive adhesive compositions, such as hot melt pressure sensitive adhesive compositions, and laminates using the compositions are disclosed. Specifically, hot melt pressure sensitive adhesive compositions, comprising: a polyol ester; a styrene- isoprene-styrene block copolymer; a cling agent; a photoinitiator; and a naphthenic oil; or a composition comprising: a styrene-isoprene-styrene block copolymer; a polybutene polymer; a photoinitiator; and a tackifier; and related laminate and label constructions thereof are discussed herein.

Description

HOTMELT ADHESIVE

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] The present application claims the benefit of U.S. Provisional Application No. 63/481,613 filed on January 26, 2023, which is incorporated herein by reference in its entirety.

TECHNICAL FIELD

[0002] This disclosure generally relates to a hot melt adhesive. More specifically hot melt pressure sensitive adhesive compositions, comprising: a polyol ester; a styrene-isoprene-styrene block copolymer; a cling agent; a naphthenic oil; and a photoinitiator; or a composition comprising: a styrene-isoprene- styrene block copolymer; a polybutene polymer; a photoinitiator; and a tackifier; and related laminate and label constructions thereof using the compositions described herein.

BACKGROUND

[0003] Pressure-sensitive adhesives have been used for a variety of applications such as labelling, packaging and other assembly purpose. Pressure-sensitive adhesives are materials which require no activation and adhere with no more than applied finger pressure are aggressive and permanently tacky at room temperature. The majority of pressure-sensitive hotmelt formulations are also tacky below room temperature and can be tacking above their glass transition temperature.

[0004] Typically, the pressure-sensitive adhesives involve solution/solvent based adhesives, water/emulsion-based adhesives, and hot-melt adhesives. The use of solvent based pressure sensitive adhesive is reduced, owing to their disadvantages including complex recycling of solvents, emission of solvents to the environment, workplace hazards due to highly flammable solvents. Similarly, use of the water-based pressure sensitive adhesive is also associated with many drawbacks. The water-based pressure sensitive adhesive requires removal of water, leading to energy intensive process. Evaporation of water also results in the uneven coating of the adhesive, and the restriction on coating speed imposed by the drying of the adhesive composition. [0005] Therefore, solvent-free technologies for producing PSA are increasing in importance. Particularly, the hot melt pressure sensitive adhesives are highly desirable, as the absence of solvent or water in the adhesive formulation lowers the energy required to form the adhesive layer and reduces the environmental problems associated with solvent-borne adhesives. Hot melt pressure sensitive adhesives are widely used for packaging applications, where high melt viscosities, leading to high adhesive strength is preferred. However, for labelling applications low melt viscosity, and quick stick performance are desirable features, and therefore, the use of hot melt pressure sensitive adhesives for labelling applications require a different formulation approach.

[0006] There is, therefore, a need to provide an improved hot melt pressure sensitive adhesive composition that exhibit excellent adhesive performance in label applications and is economical.

SUMMARY

[0007] Exemplary embodiments relate to a composition, comprising: a polyol ester; a styrene- isoprene-styrene block copolymer; a cling agent; a photoinitiator; and a naphthenic oil. This embodiment or another exemplary embodiment may provide for an antioxidant. This embodiment or another exemplary embodiment may provide the photoinitator is present in the composition at about 1.8% by weight percentage by weight of the composition. This embodiment or another exemplary embodiment may provide for a first plasticizer. This embodiment or another exemplary embodiment may provide for a block copolymer having 25% styrene content by weight, and 17.5% polystyrene by weight, and butadiene. This embodiment or another exemplary embodiment may provide for an elastomer with a polystyrenepolyisoprene block structure. This embodiment or another exemplary embodiment may provide for the polyol ester is a pentaerythritol-esterfied rosin. This embodiment or another exemplary embodiment may provide for the cling agent comprises isotactic propylene repeat units with random ethylene distribution. This embodiment or another exemplary embodiment may provide for a percentage of the polyol ester is between about 35% and about 50% by weight; a percentage of the styrene-isoprene-styrene block copolymer is between about 10% and about 40% by weight; and a percentage of the naphthenic oil is between about 10% and about 25% by weight. This embodiment or another exemplary embodiment may provide for a laminate, comprising: a facestock layer; wherein the facestock layer has a first side and a second side; an adhesive layer comprising a composition comprising a polyol ester; a styrene-isoprene-styrene block copolymer; a cling agent; and a naphthenic oil is applied to at least a portion of the second side of the facestock layer after being cured.

[0008] A further exemplary embodiment relates to a composition, comprising: a styrene-isoprene-styrene block copolymer; a polybutene polymer; a photoinitiator; and a tackifier. This embodiment or another exemplary embodiment may provide for the tackifier comprises cycloaliphatic hydrocarbon resins. This embodiment or another exemplary embodiment may provide for an antioxidant. This embodiment or another exemplary embodiment may provide for the photoinitator is present in the composition at about 1.3% by weight percentage by weight of the composition. This embodiment or another exemplary embodiment may provide for a laminate, comprising: a facestock layer; wherein the facestock layer has a first side and a second side; an adhesive layer comprising the composition of a styrene-isoprene-styrene block copolymer; a polybutene polymer; and a tackifier after being cured, wherein the tackifier comprises cycloaliphatic hydrocarbon resins and is applied to at least a portion of the second side of the facestock layer. This embodiment or another exemplary embodiment may provide for the tackifier comprises an aromatic modified aliphatic hydrocarbon resin. This embodiment or another exemplary embodiment may provide for the tackifier has a molecular weight average (M_w) between about 1600 g/mol and 2800 g/mol. This embodiment or another exemplary embodiment may provide for an antioxidant. This embodiment or another exemplary embodiment may provide for the photoinitator is present in the composition at about 1.3% by weight percentage by weight of the composition. This embodiment or another exemplary embodiment may provide for a laminate, comprising: a facestock layer; wherein the facestock layer has a first side and a second side; an adhesive layer comprising the composition of a styrene-isoprene-styrene block copolymer; a polybutene polymer; and a tackifier, wherein the tackifier comprises an aromatic modified aliphatic hydrocarbon resin and is applied to at least a portion of the second side of the facestock layer after being cured.

BRIEF DESCRIPTION OF THE DRAWINGS

[0009] The accompanying drawings, which are included to provide a further understanding of the exemplary embodiments and are incorporated in and constitute a part of this specification, illustrate various embodiments of the exemplary embodiments and together with the description serve to explain the principles of the disclosure. As will be realized, the subject matter described herein is capable of other and different embodiments and its several details are capable of modifications in various respects, all without departing from the claimed subject matter. Accordingly, the drawings and description are to be regarded as illustrative and not restrictive. In the drawings:

[0010] Figure 1 illustrates an exemplary embodiment of a laminate construction as described herein, including the facestock layer, pressure sensitive adhesive layer, and optional release layer described herein.

[0011] Figure 2 illustrates an exemplary embodiment of a laminate construction as described herein, including the he facestock layer, pressure sensitive adhesive layer, and optional release layer, optional coating, and optional printed indicia described herein.

Definitions

[0012] As used herein, "hot melt pressure sensitive adhesive" means a pressure sensitive adhesive that contains a thermoplastic material which state sticks to a substrate.

[0013] As used herein, the term "label" means a two-dimensional piece of paper, fabric, plastic, or similar material configured to be attached to an object and giving information about it and/or decoration to it. The label may be any suitable shape or design, such as, for example, rectangular, square, circular, oval, triangular, multisided and irregular shapes. The label may have edges and corners that are sharp, rounded, or irregular. Labels may be formed from the laminates described herein with printed indicia thereon.

[0014] As used herein, the term "facestock layer" means a layer or multiple layers of film material (such as paper, polymeric film, metallic foil, or combinations thereof) to which printed indicia is added and which optionally be corona treated. The facestock layer has two sides, including the first side that is outward facing and that can receive printed indicia and the other second side that is inward facing and that can receive the adhesive layer. [0015] As used herein, the term "adhesive layer" means a layer or multiple layers of the same or different hot melt pressure sensitive adhesives applied to a portion of the second surface of the facestock layer.

[0016] As used herein, the phrase "release liner" means film sheet (typically paper or polymeric film, usually applied during the manufacturing process) used to prevent a sticky surface from prematurely adhering. It is coated on one or both sides with a release agent, which provides a release effect against any type of a sticky material, such as an adhesive or a mastic.

[0017] As used herein, the phrase "printed indicia" means any string of alphanumeric or special characters used to convey information (such as name, residence or mailing address, telephone number, prescription number, and the like) and/or provide aesthetic appeal. The indicia may be printed in any suitable means including printing by hand, typewriter, or convention printing (such as flexographic printing, offset printing, inkjet printing, laser inkjet printing, videojet printing, thermal transfer, direct printing, gravure printing, and the like).

[0018] The term "coating" as used herein refers to a coating disposed on and in direct contact with an underlying backing film or other layer.

DETAILED DESCRIPTION

[0019] Novel compositions, particularly pressure sensitive adhesive compositions, such as hot melt pressure sensitive adhesive compositions, and laminates using the compositions are disclosed.

Specifically, hot melt pressure sensitive adhesive compositions, comprising: a polyol ester; a styrene- isoprene-styrene block copolymer; a cling agent; and a naphthenic oil; or a composition comprising: a styrene-isoprene-styrene block copolymer; a polybutene polymer; and a tackifier; and related laminate and label constructions thereof are discussed herein.

Adhesives [0020] The laminates/constructs described herein contain one or more adhesives. The adhesive(s) can be a pressure sensitive adhesive (PSA), a non-pressure sensitive adhesive, a hot-melt adhesive, or combinations thereof. In some embodiments, the adhesive is a PSA. The PSA may be any known PSA. In some embodiments, the PSA is a solvent type adhesive, an emulsion type adhesive, or non-emulsion type adhesive. In some embodiments, the PSA is an emulsion adhesive. Hot melt PSAs may also be used. The adhesive may be acrylic or any other useful adhesive which has the hardness and adhesive properties needed for the laminates and/or adhesive coated facestocks. In certain embodiments, the adhesive should have a hardness sufficient to prevent the adhesive squeezing out of the laminate or article during processing.

[0021] Exemplary PSAs may be found in (1) Encyclopedia of Polymer Science and Engineering, Vol. 13, Wiley-lnterscience Publishers (NewYork, 1988); (2) Polymer Science and Technology, Vol. 1, Interscience Publishers (New York, 1964); (3) those described in U.S. Pat. Nos. 5,164,444; 5,183,459; and 5,264,532, all issued to Bernard, and U.S. Pat. No. 5,385,965, issued to Bernard et al; and (4) combinations thereof. The PSAs may be a solvent based or may be a water based adhesive. Conventional PSAs, including acrylic-based PSAs, rubber-based PSAs and silicone-based PSAs may be used in the laminates/constructs described herein. In one embodiment, the pressure sensitive adhesive contains an acrylic emulsion adhesive.

[0022] In exemplary embodiments, the coat weight of adhesives may be between 2 and 100 gsm.

[0023] Accordingly, one exemplary embodiment is directed to compositions, particularly pressure sensitive adhesive compositions, such as hot melt pressure sensitive adhesive compositions, comprising: a polyol ester; a styrene-isoprene-styrene block copolymer; a cling agent; and a naphthenic oil. Hot melt pressure sensitive adhesives tend to not be used within high performance applications is they generally have poor performance when subjected to high temperatures or other solvents. Additionally, higher coat weights of hot melt adhesives tend to have bleeding issues, which leads to a lot of problems during diecutting or slitting. Thus, crosslinked rubber based hot melt adhesives described herein could be solutions to the above limitations. All formulations can be free any mineral oil.

[0024] In yet other embodiments of the composition, is directed to a composition comprising: a styrene-isoprene-styrene block copolymer; a polybutene polymer; and a tackifier. [0025] The compositions of the exemplary embodiments may further comprise additives such as pigments, colors or colorants, fillers, diluents, antioxidants, UV absorbers, and the like, and combinations thereof, provided that their inclusion do not impact the adhesive performance properties, safety profile of the label, and recyclability.

[0026] Pigment, if desired, is provided in an amount sufficient to impart the desired color to the adhesive. Examples of pigments include, without limitation, solid inorganic fillers such as carbon black, titanium dioxide and the like, and organic dyes.

[0027] Antioxidants also may be included in the compositions. Cutting agents such as waxes and surfactants also may be included in the adhesives. Light stabilizers, heat stabilizers, and UV absorbers also may be included in the adhesive compositions. A photoinitiator is included in exemplary embodiments. Ultraviolet absorbers include benzo-triazol derivatives, hydroxy benzyl phenones, esters of benzoic acids, oxalic acid, diamides, and the like. Light stabilizers include hindered amine light stabilizers, and the heat stabilizers include dithiocarbamate compositions such as zinc dibutyl dithiocarbamate.

[0028] In exemplary embodiments, the polyol ester is between about 35% and about 50% by weight. The polyol ester may also be a tackifier. One such polyol ester contemplated by the exemplary embodiments is a pentaerythritol-esterfied resin. One such polyol ester of this nature is sold under the name Dertoline PLS a deodorized and highly stabilized pentaerythritol-esterified rosin, is a tackifier resin produced and distributed by the company DRT SA, headquartered in Bordeaux, France.

[0029] In some exemplary embodiments, the styrene-isoprene-styrene block copolymer is between about 10% and about 40% by weight. One such styrene-isoprene-styrene block copolymer contemplated is the styrene-isoprene-styrene (SIS) block copolymer system allows heat-resistant, photo-cured crosslinking, serving to eliminate the tradeoffs between hot-melt SIS systems and solvent-based SIS rubber systems sold as Zeon SL-177 sold by Nippon Zeon headquartered in Tokyo, Japan.

[0030] In some exemplary embodiments, the cling agent is between about 0.1% to about 2% by weight. One such cling agent contemplated is primarily composed of isotactic propylene repeat units with random ethylene distribution and sold under the name Vistamaxx 6202 sold by ExxonMobil, headquartered in Irving, Texas, USA.

[0031] In some exemplary embodiments the naphthenic oil is between about 10% and 25% by weight. One such naphthenic oil contemplated is a highly refined, high viscosity oil that is sold under the name Nyflex 223 sold by Nynas AB, headquartered in Stockholm, Sweden and Primol 352 sold by ExxonMobil, headquartered in Irving, Texas, USA. In certain embodiments, the naphthenic oil could be replaced with a plasticizing oil. The plasticizing oil could be naphthenic, paraffinic mineral oil, or white medicinal oil.

[0032] In some exemplary embodiments the antioxidant is between about 0.01% and about 1.5% by weight. One such antioxidant contemplated is tetrakis[methylene-3-(3,5-di-tert-butyl-4- hydroxyphenyl)propionate] methane and tris(2,4-di-tert-butyl phenyl) phosphite (1:2) sold under the name Songnox® 21B by Songwon, headquartered in Ulsan, Korea.

[0033] In some exemplary embodiments, an additional block copolymer can be used. When used, the additional block copolymer is between about 10% and about 25% by weight. In some embodiments this could be a linear random-block styrene/butadiene copolymer having 25% of styrene content, 17.5% present as a polystyrene block sold under the name Solprene 1205 by Dynasol Elastomers headquartered in Houston, Texas, USA. In other embodiments the additional block copolymer could be thermoplastic elastomers with polystyrene-polyisoprene block structures between about 20% and about 35% sold under the name Quintac 3270 sold by Nippon Zeon headquartered in Tokyo, Japan. Other embodiments may provide for a mix of a linear random-block styrene/butadiene copolymer having 25% of styrene content, 17.5% present as a polystyrene block and thermoplastic elastomers with polystyrene- polyisoprene block with a percentage between about 20% and about 37%.

[0034] In some exemplary embodiments, the photoinitator is between about 0.25% and about 5% by weight. One such photoinitator contemplated by the exemplary embodiments is 2-hydroxy-l-[4-[4-(2- hydroxy-2-methylpropionyl)benzyl)phenyl)-2-methylpropan-l-one, sold under the name Omnirad 127D by IGM Resin b.v. out of Waalwijk, Netherlands. Another such example of a photoinitiator contemplated by the exemplary embodiments is a difunctional alpha hydroxy ketone, specifically, 2-hydroxy-l-{4-[4-(2- hydroxy-2-methylpropanoyl)phenoxy]phenyl}-2-methylpropan-l-one sold under the name Esacure KIP

160 also by IGM Resin b.v. out of Waalwijk, Netherlands.

[0035] In some embodiments, the resultant hot melt pressure sensitive adhesive is crosslinked. When it is crosslinked, a free radical is generated from the photoinitiator and an energy source. Specific embodiments use an ultraviolet (UV) light, and other embodiments specifically use UV-C light with a wavelength between 100-280 nm. In order to obtain the desired amount of crosslinking, various different photointiiators may be used and different doses of UV-C radiation can be used. In the exemplary embodiment, a dose between 5 and 150 mJ/cm² is used. However, the ultimate use of the radiation depends on the desired implementation of the resultant adhesive.

[0036] In some exemplary embodiments, the polybutene polymer is between about 15% to about 25% by weight. A few exemplary polybutene polymers are a liquid polybutene homopolymer, sold under the name Indopol H-100, Indopol H-300 supplied by INEOS Olefins & Polymers USA out of League City, Texas, USA. These polybutene polymers may be used alone, or in combination.

[0037] In exemplary embodiments, a separate tackifier may be used. The tackifier can be between about 40% and about 55% weight percentage. Two such contemplated tackifiers are cycloaliphatic hydrocarbon resins sold as Escorez 5300 and an aromatic modified aliphatic hydrocarbon resin with a narrow molecular weight distribution sold as Escorez 2203 both sold by ExxonMobil, headquartered in Irving, Texas, USA. The tackifier with the aromatic modified aliphatic hydrocarbon resin with the narrow molecular weight distribution has a molecular weight average (M_w) between about 1600 g/mol and 2800 g/mol.

Release Liners

[0038] In some embodiments, the laminates described herein may include one or more release liner(s). The liner may have a first side, a second side opposed to the first side, a first edge, and a second edge opposed to the second edge. The liner may be any useful liner which provides necessary support and release properties. The liner may be made of, or from, a variety of materials including, but not limited to, paper or polymer film liners. In one embodiment, the caliper of the paper is sufficient to die cut the resulting laminate or article. For example, liner calipers can range from about 18 mm to 23 mm for PET liners. In one embodiment, the liner has lay flat properties. In some embodiments, the liner has a machine glaze or finish. In some embodiments, the liner has a silicone hold out layer. The hold out layer provides adhesion between the release coating and the release liner. The silicone holdout layer also prevents the silicone release coating from soaking into the liner.

[0039] In some embodiments, the release liner includes a liner having a release coating. The release coating of the release liner provides a releasable bond with the PSA or other adhesive. The release coating may be any composition which provides a desired releasable bond strength.

[0040] In one embodiment, the release coating is a silicone release coating. The release coating can be prepared by curing silicone polymers in the presence of a control release agent. In some embodiments, the control release agent is a copolymer of a monofunctional silicone unit of the formula R₃SiOi/₂ and tetrafunctional silicone units SiO₄/2 wherein R is an alkyl or alkenyl group. In one embodiment, the alkyl or alkenyl groups contain from about 1 to about 12, or from about 1 to about 6 carbon atoms. Non-limiting examples of alkyl and alkenyl groups include methyl, ethyl, propyl, butyl, hexyl, ethenyl, propenyl, butenyl and hexenyl groups.

[0041] The control release agent is typically reacted with a polysiloxane. The polysiloxane may be any polysiloxane which is useful in forming a release coating. Examples of useful polysiloxanes include, but are not limited to, vinyl terminated, hydroxy terminated and epoxy terminated polysiloxanes. In one embodiment, the polysiloxane is a functional polydialkyl siloxane, wherein the alkyl group contains from about 1 to about 6 carbon atoms. The alkyl groups independently include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl groups or mixtures thereof. In one embodiment, the alkyl or alkenyl group contains from 1 to about 12, or from 1 to about 6 carbon atoms. The polysiloxane typically has a viscosity average molecular weight of greater than 300,000 centipoise (cps). In another embodiment, the polysiloxane has a viscosity molecular weight from about 300,000 to about 1,000,000 or more. The polysiloxane may be represented by the formula (I): RO((Si(R)₂O)_x)-Si)-R (I) wherein each R is independently as defined above and x is an integer. [0042] In some embodiments, the release coating is prepared with a cross linking agent. In some embodiments, the cross linking agent is a reactive polysiloxane, such as a polydialkyl or polyhydroalkyl siloxane. The alkyl groups are the same as those described above.

[0043] The release coating may be applied in a solvent, solvent-less or emulsion form. The release coating may be cured by any known curing process, e.g. thermal, radiation, etc., to form the release coating. The curing may be catalyzed by silicone soluble complexed compounds of Group VIII transition metals, such as platinum.

[0044] Commercially available release agents include, but are not limited to, GE SS-4335, a silicone release agent in unreactive solvent. Commercially available polysiloxanes include, but are not limited to, GE SS-4331, a vinyl terminated polydimethyl siloxane. Commercially available linking agents include, but are not limited to, GE SS-4300C, a polymethyvinyl siloxane. Exemplary catalysts include, but are not limited to, SS-8010 catalyst in toluene. These materials are available commercially from General Electric Company's Silicone Products Division. Similar silicone products are available under the tradename Syl-off from Dow Corning Corporation.

[0045] It will be understood that the present subject matter is not limited to any of the noted release coatings or agents, and instead includes nearly any release coating or agent suitable for the intended end use application. Furthermore, although the present subject matter has been described in association with release liners, it will be appreciated that appropriately configured carrier films and other members could be used instead of release liners.

Face Material

[0046] Suitable face materials include, but are not limited to, synthetic papers such as polyolefin type and polystyrene type; various plastic films or sheets such as polyolefin, polyvinyl chloride, polyethylene terephthalate, polystyrene, polyurethane, polymethacrylate and polycarbonate. Additional examples of suitable face materials include paper and cardboard. The face material may be, or may include, a multilayer polymeric sheet. The multi-layers may be coextruded, or the multi-layers may be laminated together. In one embodiment, the face material includes both co-extruded multi-layers and laminated multi-layers. In addition, a white opaque film may be formed by adding a white pigment to one or more of the aforementioned synthetic resins and used as the face material. In one embodiment, a foamed film is used as the face material. The foamed film may be formed by a conventional foaming operation. In another embodiment, the face material may be a laminated body formed by combining a plurality of single layered sheets composed of the above listed materials. Examples of such a laminated body may include the combination of cellulose fiber paper with synthetic paper, and a laminated body of combined cellulose fiber paper with a plastic film or sheet. In another suitable embodiment, the face material includes coated and uncoated papers, metalized papers, aluminum foil, laminated paper and paper with a polymeric material extruded onto the surface of the paper. In certain versions, the face material can be coated with a liquid absorbent material. The selected face material may be porous or semi-porous. The face material may exhibit certain visibility characteristics such as opaqueness, color, and/or brightness. The face material may include water or other liquid absorbency properties. The face material may be electrically conductive and/or include electrically conductive coatings or regions. A wide array of commercially available face materials can be used such as for example those available under the designation TESLIN.

[0047] The thickness of the face material is optionally determined with reference to application specific criteria. Such criteria may include the desired end use. In one embodiment, the sheet thickness is in a range of from about 10 pm to about 300 pm. In another embodiment, the sheet thickness is in a range of from about 20 pm to about 200 pm. In still another embodiment, the sheet thickness is in a range of from about 30 pm to about 150 pm. Optionally, a primer treatment or a corona discharging treatment or a plasma treatment may be used on the face material to increase a bonding strength between the face material and a dried topcoat composition to be formed on a surface of the face material.

[0048] In certain embodiments described herein, the face material exhibits one or more functions or functional characteristics. For example, the face material may be selected to enable or promote an indication such as a visual indication of a liquid, outgassing such as directing or allowing flow of air or gas across a thickness of the face material, water or liquid retention within the face material, electrical discharge or conductivity of the face material, chemical delivery across a thickness of the face material, passage of sound across a thickness of the face material, and/or combinations of these functions or characteristics.

Optional Layers

[0049] The adhesive coated face material and/or laminates described herein can include one or more additional layers or components. Non-limiting examples of such layers include protective layers, tie coat layers, clear layers, color layers, white layers, reflective layers, fluid transfer layers, strength promoting layers, topcoats, print receptive layers, print containing layers, indicia layers, functional layers, barrier coatings, and the like.

Laminate Properties

[0050] The laminates described herein may have specific and useful properties or functionalities. In some embodiments, the techniques described herein enable formation of laminates in which transfer, propagation, and/or migration of liquid, gas, sound waves, electrical current, and/or other agents or elements can occur and is controlled across or through the laminate in a Z-direction. The reference to "Z- direction" as made herein refers to a direction across a thickness dimension of a laminate or portion thereof, and thus references to "X-direction" and/or "Y-direction" refer to directions perpendicular to the Z-direction and correspond to width and length dimensions of the laminate.

[0051] Non-limiting representative examples of laminates having certain functionalities which are provided by the present subject matter include liquid indicator laminates, outgassing laminates, water absorbent laminates, sound channeling laminates, electrically conductive laminates, and laminates having combinations of these functionalities and/or laminates having combinations of one or more of these functionalities and additional functionalities.

[0052] For example, a liquid indicator laminate can be produced such that the speed of the indicator color change is linked to the facestock selection and porous adhesive properties. A discontinuous structure, such as resulting from pores in the adhesive layer or region(s), can allow, for example, liquid to channel through the discontinuous adhesive from one side of the adhesive to the other side and create a permanent discoloration when a dye or other agent in a functional coating in the laminate is dissolved. [0053] In one embodiment, a liquid indicator laminate is provided. The speed or rate of the indicator color change is linked to the facestock properties such as for example absorbency of liquid, and porosity of the pattern adhesive in the Z-direction. The indication typically is irreversible and can be measured by color change or by a simple visual comparison.

[0054] The discoloration of a face or region of the laminate can be measured and quantified by optical change, such as by CIE Lab or by a simple visual comparison. The discoloration can be permanent or nonpermanent. The discoloration can also be temporary and revert to an initial state after passage of a period of time. In some embodiments, the period of time is predetermined.

[0055] This phenomenon of transport through discontinuities in an adhesive in the Z-direction can be implemented in other label applications and particularly pressure sensitive adhesive labels, such as for example, labels for outgassing substrates such as by air channeling in the Z-direction, moist substrate labeling such as by liquid channeling in the Z-direction, electrical discharge in the Z-direction, chemical delivery from one layer to another in the Z-direction, and/or sound channeling in the Z-direction. This phenomenon enables passage, transfer, and/or migration of a medium or agent from one side of an adhesive region of a laminate, to another side of the adhesive region. Although medium penetration or transport is noted as being in the Z-direction, it will be understood that the present subject matter is not limited to such and may also include penetration/transport in the X-direction and/or Y-direction.

[0056] In some embodiments, the laminates described herein include a layer or region of a secondary adhesive. The secondary adhesive is typically utilized to adhere the laminate to a substrate of interest. The secondary adhesive may contain one or more adhesives which are the same or different than the adhesive of the patterned or porous adhesive. Description of representative examples of secondary adhesives are provided herein. In such an adhesive configuration, the primary adhesive may be coated onto the facestock, the secondary adhesive may be coated onto the release liner, and the coated adhesive and release liner may be laminated together such that the primary and secondary adhesives are in direct contact with each other. Alternatively, or additionally, both the primary and secondary adhesive may be coated on the facestock or the release liner, then laminated together. It is contemplated that the layering of the primary and secondary adhesive relative to the facestock and the release liner may be either facestock, primary adhesive, secondary adhesive, and release liner or facestock, secondary adhesive, primary adhesive, release liner. Regardless of the order of primary and secondary adhesive, it is contemplated that at least one of the primary and secondary adhesive is patterned, taking into consideration that the other adhesive may be continuous.

[0057] In some embodiments, an array of different arrangements of layers and components may be utilized. In some embodiments using the patterned adhesive, e.g., the layer of discontinuous adhesive, that layer is disposed between a functional facestock and a liner or functional layer. And in the liquid indicator laminates, the patterned adhesive may be disposed between the functional facestock and the layer or region of functional agent that is sensitive to liquid passing through the laminate. And, in the liquid indicator laminates, the layer or region of the functional agent may be disposed between the patterned adhesive and the carrier layer.

[0058] Utilization of the techniques and features described herein enable production of adhesive laminates and/or adhesive coated face materials with fluid/air management characteristics, controlled removability, and/or unique thermal and/or electrical conductivity. In addition, use of these techniques and features enable reductions in materials, e.g., adhesives, and thus enable cost savings. However, it will be understood that the present subject matter includes the adhesive coated face materials and laminates described herein which are formed by other methods than the methods described herein.

[0059] Another embodiment is directed to laminates, comprising: a facestock layer comprising paper; wherein the facestock layer has a first side and a second side; and an adhesive layer comprising the pressure adhesive compositions described herein applied to at least a portion of the second side of the facestock layer. The thickness of the facestock typically ranges from 10 pm to 250 pm, preferably 30 pm to 220 pm. The thickness of the adhesive layer typically ranges from 5 pm to at least 125 pm, preferably 10 pm to at least 100 pm. In certain embodiments, the laminate further comprises a release layer on the adhesive layer on the side opposite to the facestock layer. In certain embodiments, the laminate further comprises printed indicia on the first side of the facestock layer. [0060] In some embodiments, the facestock layer used in the laminate constructions may be coated with one or more coating layers. Typically, coatings are initially in a liquid or flowable state; deposited or applied on the underlying backing film or other layer; and then cured or otherwise solidified. For applications in which the coating is formed into a film, the film is typically independent from an underlying film or other layer. In many versions, backing films as described herein are free standing films. However, films formed from the coating as described herein may be positioned alongside or in conjunction with the backing film or other layers. The coating may have a thickness or coating weight greater than 1 gsm and typically within a range of from 1 gsm to 30 gsm. In certain embodiments, the coatings have a thickness or coating weight within a range of from 5 gsm to 30 gsm. However, it will be understood that the coatings may have thicknesses or coating weights less than 1 gsm, and/or greater than 30 gsm.

[0061] Coatings useful in the exemplary embodiments can be formed using a wide array of techniques. Upon depositing the composition upon a surface of interest, the layer of composition dries, hardens, and/or otherwise cures to form a coating. After deposition of the composition and during or after formation of the coating, one or more post-deposition treatments may be utilized such as exposure to radiation or heat. In some embodiments, the coatings or films undergo crosslinking during preparation or deposition.

[0062] The compositions useful in the laminate construction may be formed into a single layer or contain multiple layers of adhesive. The multiple layers of adhesive may be applied to the film or laminate simultaneously using methods known in the art. Examples of suitable adhesive coating methods include slot die coating, bullnose coating, reverse roll coating and the like.

[0063] The release layer that may be utilized in the useful in the laminate construction of the invention may contain any of a variety of materials known to those of skill in the art to be suitable as release liners. In one embodiment, the release liner contains or is a 90# stayflat liner. Other suitable release liners include silicone coated films or polycoated kraft paper, as are known in the art. Suitable pre-siliconized release liners are available commercially. The release liner may be flat or structured.

Top Coat Formulation and Application [0064] In exemplary embodiments discussed herein, the top coat coating is deposited on the substrate by any suitable method. In embodiments, the suitable method includes any suitable coating technology. Embodiments include depositing the coating on the substrate by any suitable liquid deposition method. Without limitation, examples of suitable methods include bath coating, spray coating, slot coating, spin coating, curtain coating, gravure coating, reverse gravure print coating, reverse roll coating, knife over roll (i.e., gap) coating, metering (Meyer) rod coating, air knife coating, or any combinations thereof. Bath coating includes immersion or dip in the aqueous solution. In an embodiment, the coating is deposited by bath in the aqueous solution. In other embodiments, the coating is deposited by spray of the aqueous solution.

Methods and Exemplary Constructions

[0065] Having discussed various components of the composition, exemplary methods and methodologies of operation will be discussed.

[0066] Figure 1 illustrates a laminate construction as described herein. The laminate construction 100 includes a facestock layer 10, pressure sensitive adhesive layer 20, and optional release layer 30, as described herein (and not shown to scale). The facestock layer 10 defines a first side 12 and an oppositely directed second side 14. The facestock layer is shown as a single layer but may be multilayer. The pressure sensitive adhesive layer 20 is applied over at least a portion of the second side 14. The pressure sensitive adhesive layer is shown as a single layer but may be multilayer.

[0067] Figure 2 illustrates a laminate construction as described herein. The laminate construction 200 includes a facestock layer 10 (paper, for example), pressure sensitive adhesive layer 20, optional release layer 30, optional printed indicia 40 (such as turbo, latex, UV, or eco-sol ink, for example), optional coating layer 50 and an optional transfer tape 60 (such as a paper transfer tape), as described herein (and not shown to scale). The facestock layer 10 defines a first side 12 and an oppositely directed second side 14. The backing film is shown as a single layer but may be multilayer. The pressure sensitive adhesive layer 20 is applied over at least a portion of the second side 14. The pressure sensitive adhesive layer is shown as a single layer but may be multilayer.

Examples

[0068] Hot melt pressure sensitive adhesive formulations were prepared with compositions as shown in the following examples. All percentages are given as a weight percentage. Each of these is a curable composition when subject to UV light that will activate the photoinitator and subsequently promote crosslinking in the cured product. These may be formulated and cured on the substrate or cured prior to application to the desired substrate, as will be known depending on the desired implementation of the various substrates.

Family A - Examples 1-4 Recycling Compatible Adhesives

Example 1

[0069] Example 1 was prepared using 42.9% of the polyol ester, 21.1% of a styrene-isoprene- styrene block copolymer, 17.2% of a naphthenic oil, 15.5% of a thermoplastic elastomer with polystyrenepolyisoprene block structures, 1.9% of photoinitiator, 1% of a cling agent, and 0.6% of an antioxidant.

Example 2

[0070] Example 2 was prepared using 42.9% of the polyol ester, 21.1% of a linear random-block styrene/butadiene copolymer having 25% of styrene content, 17.5% present as a polystyrene block, 17.2% of a naphthenic oil, 15.5% of a styrene-isoprene-styrene block copolymer, 1.9% of photoinitiator, 1% of a cling agent, and 0.6% of an antioxidant.

Example 3 [0071] Example 3 was prepared using 42.9% of the polyol ester, 21.1% of a of a styrene- isoprene-styrene block copolymer, 17.2% of a naphthenic oil, 15.5% of a thermoplastic elastomer with polystyrene-polyisoprene block structures, 1.9% of photoinitiator, 1% of a cling agent, and 0.6% of an antioxidant.

Example 4

[0072] Example 4 was prepared using 42.9% of the polyol ester, 36.6% of a styrene-isoprene- styrene block copolymer, 17.2% of a naphthenic oil, 1.9% of photoinitiator, 1% of a cling agent, and 0.6% of an antioxidant.

Family B - Solvent Replacement Adhesives - Examples 5-28

Example 5

[0073] Example 5 was produced using 35% of a tackifier in the form of a compound comprising cycloaliphatic hydrocarbon resins, 27% of a styrene-isoprene-styrene block copolymer, 35% of a polybutene polymer, 1.3% of a photoinitiator, and 0.7% of an antioxidant.

Example 6

[0074] Example 6 was produced using 35% of a tackifier in the form of a compound comprising cycloaliphatic hydrocarbon resins, 35% of a styrene-isoprene-styrene block copolymer, 27% of a polybutene polymer, 1.3% of a photoinitiator, and 0.7% of an antioxidant.

Example 7 [0075] Example 7 was produced using 39% of a tackifier in the form of a compound comprising cycloaliphatic hydrocarbon resins, 27% of a styrene-isoprene-styrene block copolymer, 31% of a polybutene polymer, 1.3% of a photoinitiator, and 0.7% of an antioxidant.

Example 8

[0076] Example 8 was produced using 39% of a tackifier in the form of a compound comprising cycloaliphatic hydrocarbon resins, 27% of a styrene-isoprene-styrene block copolymer, 31% of a polybutene polymer, 1.3% of a photoinitiator, and 0.7% of an antioxidant.

Example 9

[0077] Example 9 was produced using 42% of a tackifier in the form of a compound comprising cycloaliphatic hydrocarbon resins, 20% of a styrene-isoprene-styrene block copolymer, 35% of a polybutene polymer, 1.3% of a photoinitiator, and 0.7% of an antioxidant.

Example 10

[0078] Example 10 was produced using 42% of a tackifier in the form of a compound comprising cycloaliphatic hydrocarbon resins, 35% of a styrene-isoprene-styrene block copolymer, 20% of a polybutene polymer, 1.3% of a photoinitiator, and 0.7% of an antioxidant.

Example 11

[0079] Example 11 was produced using 42% of a tackifier in the form of a compound comprising cycloaliphatic hydrocarbon resins, 24% of a styrene-isoprene-styrene block copolymer, 31% of a polybutene polymer, 1.3% of a photoinitiator, and 0.7% of an antioxidant.

Example 12 [0080] Example 12 was produced using 42% of a tackifier in the form of a compound comprising cycloaliphatic hydrocarbon resins, 31% of a styrene-isoprene-styrene block copolymer, 24% of a polybutene polymer, 1.3% of a photoinitiator, and 0.7% of an antioxidant.

Example 13

[0081] Example 13 was produced using 42% of a tackifier in the form of a compound comprising cycloaliphatic hydrocarbon resins, 27% of a styrene-isoprene-styrene block copolymer, 27% of a polybutene polymer, 1.3% of a photoinitiator, and 0.7% of an antioxidant.

Example 14

[0082] Example 14 was produced using 50% of a tackifier in the form of a compound comprising cycloaliphatic hydrocarbon resins, 24% of a styrene-isoprene-styrene block copolymer, 24% of a polybutene polymer, 1.3% of a photoinitiator, and 0.7% of an antioxidant.

Example 15

[0083] Example 15 was produced using 57% of a tackifier in the form of a compound comprising cycloaliphatic hydrocarbon resins, 20% of a styrene-isoprene-styrene block copolymer, 20% of a polybutene polymer, 1.3% of a photoinitiator, and 0.7% of an antioxidant.

Example 16

[0084] Example 16 was produced using 35% of a tackifier in the form of a compound comprising cycloaliphatic hydrocarbon resins, 27% of a thermoplastic elastomer with polystyrene-polyisoprene block structures, 35% of a polybutene polymer, 1.3% of a photoinitiator, and 0.7% of an antioxidant.

Example 17 [0085] Example 17 was produced using 35% of a tackifier in the form of a compound comprising cycloaliphatic hydrocarbon resins, 35% of a thermoplastic elastomer with polystyrene-polyisoprene block structures, 27% of a polybutene polymer, 1.3% of a photoinitiator, and 0.7% of an antioxidant.

Example 18

[0086] Example 18 was produced using 39% of a tackifier in the form of a compound comprising cycloaliphatic hydrocarbon resins, 27% of a thermoplastic elastomer with polystyrene-polyisoprene block structures, 31% of a polybutene polymer, 1.3% of a photoinitiator, and 0.7% of an antioxidant.

Example 19

[0087] Example 19 was produced using 39% of a tackifier in the form of a compound comprising cycloaliphatic hydrocarbon resins, 27% of a thermoplastic elastomer with polystyrene-polyisoprene block structures, 31% of a polybutene polymer, 1.3% of a photoinitiator, and 0.7% of an antioxidant.

Example 20

[0088] Example 20 was produced using 42% of a tackifier in the form of a compound comprising cycloaliphatic hydrocarbon resins, 20% of a thermoplastic elastomer with polystyrene-polyisoprene block structures, 35% of a polybutene polymer, 1.3% of a photoinitiator, and 0.7% of an antioxidant.

Example 21

[0089] Example 21 was produced using 42% of a tackifier in the form of a compound comprising cycloaliphatic hydrocarbon resins, 35% of a thermoplastic elastomer with polystyrene-polyisoprene block structures, 20% of a polybutene polymer, 1.3% of a photoinitiator, and 0.7% of an antioxidant.

Example 22 [0090] Example 22 was produced using 42% of a tackifier in the form of a compound comprising cycloaliphatic hydrocarbon resins, 24% of a thermoplastic elastomer with polystyrene-polyisoprene block structures, 31% of a polybutene polymer, 1.3% of a photoinitiator, and 0.7% of an antioxidant.

Example 23

[0091] Example 23 was produced using 42% of a tackifier in the form of a compound comprising cycloaliphatic hydrocarbon resins, 31% of a thermoplastic elastomer with polystyrene-polyisoprene block structures, 24% of a polybutene polymer, 1.3% of a photoinitiator, and 0.7% of an antioxidant.

Example 24

[0092] Example 24 was produced using 42% of a tackifier in the form of a compound comprising cycloaliphatic hydrocarbon resins, 27% of a thermoplastic elastomer with polystyrene-polyisoprene block structures, 27% of a polybutene polymer, 1.3% of a photoinitiator, and 0.7% of an antioxidant.

Example 25

[0093] Example 25 was produced using 50% of a tackifier in the form of a compound comprising cycloaliphatic hydrocarbon resins, 24% of a thermoplastic elastomer with polystyrene-polyisoprene block structures, 24% of a polybutene polymer, 1.3% of a photoinitiator, and 0.7% of an antioxidant.

Example 26

[0094] Example 26 was produced using 57% of a tackifier in the form of a compound comprising cycloaliphatic hydrocarbon resins, 20% of a thermoplastic elastomer with polystyrene-polyisoprene block structures, 20% of a polybutene polymer, 1.3% of a photoinitiator, and 0.7% of an antioxidant. Example l

[0095] Example 27 was produced using 46.5% of a tackifier in the form of a compound comprising cycloaliphatic hydrocarbon resins, 32.1% of a styrene-isoprene-styrene block copolymer, 18.8% of a polybutene polymer, 1.9% of a photoinitiator, and 0.7% of an antioxidant.

Example 28

[0096] Example 28 was produced using 46.8% of a tackifier in the form of a compound comprising cycloaliphatic hydrocarbon resins, 32.3% of a thermoplastic elastomer with polystyrenepolyisoprene block structures, 18.9% of a polybutene polymer, 1.3% of a photoinitiator, and 0.7% of an antioxidant.

[0097] All definitions, as defined and used herein, should be understood to control over dictionary definitions, definitions in documents incorporated by reference, and/or ordinary meanings of the defined terms.

[0098] The articles "a" and "an," as used herein in the specification and in the claims, unless clearly indicated to the contrary, should be understood to mean "at least one." The phrase "and/or," as used herein in the specification and in the claims (if at all), should be understood to mean "either or both" of the elements so conjoined, i.e., elements that are conjunctively present in some cases and disjunctively present in other cases. Multiple elements listed with "and/or" should be construed in the same fashion, i.e., "one or more" of the elements so conjoined. Other elements may optionally be present other than the elements specifically identified by the "and/or" clause, whether related or unrelated to those elements specifically identified. Thus, as a non-limiting example, a reference to "A and/or B", when used in conjunction with open-ended language such as "comprising" can refer, in one embodiment, to A only (optionally including elements other than B); in another embodiment, to B only (optionally including elements other than A); in yet another embodiment, to both A and B (optionally including other elements); etc. As used herein in the specification and in the claims, "or" should be understood to have the same meaning as "and/or" as defined above. For example, when separating items in a list, "or" or "and/or" shall be interpreted as being inclusive, i.e., the inclusion of at least one, but also including more than one, of a number or list of elements, and, optionally, additional unlisted items. Only terms clearly indicated to the contrary, such as "only one of" or "exactly one of," or, when used in the claims, "consisting of," will refer to the inclusion of exactly one element of a number or list of elements. In general, the term "or" as used herein shall only be interpreted as indicating exclusive alternatives (i.e. "one or the other but not both") when preceded by terms of exclusivity, such as "either," "one of," "only one of," or "exactly one of." "Consisting essentially of," when used in the claims, shall have its ordinary meaning as used in the field of patent law.

[0099] As used herein in the specification and in the claims, the phrase "at least one," in reference to a list of one or more elements, should be understood to mean at least one element selected from any one or more of the elements in the list of elements, but not necessarily including at least one of each and every element specifically listed within the list of elements and not excluding any combinations of elements in the list of elements. This definition also allows that elements may optionally be present other than the elements specifically identified within the list of elements to which the phrase "at least one" refers, whether related or unrelated to those elements specifically identified. Thus, as a non-limiting example, "at least one of A and B" (or, equivalently, "at least one of A or B," or, equivalently "at least one of A and/or B") can refer, in one embodiment, to at least one, optionally including more than one, A, with no B present (and optionally including elements other than B); in another embodiment, to at least one, optionally including more than one, B, with no A present (and optionally including elements other than A); in yet another embodiment, to at least one, optionally including more than one, A, and at least one, optionally including more than one, B (and optionally including other elements); etc.

[0100] An embodiment is an implementation or example of the present disclosure. Reference in the specification to "an embodiment," "one embodiment," "some embodiments," "one particular embodiment," or "other embodiments," or the like, means that a particular feature, structure, or characteristic described in connection with the embodiments is included in at least some embodiments, but not necessarily all embodiments, of the invention. The various appearances "an embodiment," "one embodiment," "some embodiments," "one particular embodiment," or "other embodiments," or the like, are not necessarily all referring to the same embodiments.

[0101] If this specification states a component, feature, structure, or characteristic "may",

"might", or "could" be included, that particular component, feature, structure, or characteristic is not required to be included. If the specification or claim refers to "a" or "an" element, that does not mean there is only one of the element. If the specification or claims refer to "an additional" element, that does not preclude there being more than one of the additional element.

[0102] As used herein in the specification and claims, including as used in the examples and unless otherwise expressly specified, all numbers may be read as if prefaced by the word "about" or "approximately," even if the term does not expressly appear. The phrase "about" or "approximately" may be used when describing magnitude and/or position to indicate that the value and/or position described is within a reasonable expected range of values and/or positions. For example, a numeric value may have a value that is +/-0. % of the stated value (or range of values), +/-1% of the stated value (or range of values), +/-2% of the stated value (or range of values), +/-5% of the stated value (or range of values), +/— 10% of the stated value (or range of values), etc. Any numerical range recited herein is intended to include all sub-ranges subsumed therein.

[0103] Additionally, any method of performing the present disclosure may occur in a sequence different than those described herein. Accordingly, no sequence of the method should be read as a limitation unless explicitly stated. It is recognizable that performing some of the steps of the method in a different order could achieve a similar result.

[0104] In the claims, as well as in the specification above, all transitional phrases such as

"comprising," "including," "carrying," "having," "containing," "involving," "holding," "composed of," and the like are to be understood to be open-ended, i.e., to mean including but not limited to. Only the transitional phrases "consisting of" and "consisting essentially of" shall be closed or semi-closed transitional phrases, respectively, as set forth in the United States Patent Office Manual of Patent Examining Procedures.

[0105] In the foregoing description, certain terms have been used for brevity, clarity, and understanding. No unnecessary limitations are to be implied therefrom beyond the requirement of the prior art because such terms are used for descriptive purposes and are intended to be broadly construed.

[0106] Moreover, the description and illustration of various embodiments of the disclosure are examples and the disclosure is not limited to the exact details shown or described.

Claims

CLAIMS We claim:

1. A composition, comprising: a polyol ester; a styrene-isoprene-styrene block copolymer; a cling agent; a naphthenic oil; and a photoinitiator.

2. The composition of claim 1, wherein the photoinitator is present in the composition at about 1.8% by weight percentage by weight of the composition.

3. The composition of claim 1 or 2, further comprising: a block copolymer having 25% styrene content by weight, and 17.5% polystyrene by weight, and butadiene.

4. The composition of claim 1, further comprising: an elastomer with a polystyrene-polyisoprene block structure.

5. The composition of claim 1 or 4, wherein the polyol ester is a pentaerythritol-esterfied rosin.

6. The composition of claim 1, wherein the cling agent comprises isotactic propylene repeat units with random ethylene distribution.

7. The composition of claim 1, wherein a percentage of the polyol ester is between about 35% and about 60% by weight; a percentage of the styrene-isoprene-styrene block copolymer is between about 15% and about 40% by weight; and a percentage of the naphthenic oil is between about 10% and about 25% by weight.

8. A laminate, comprising: a facestock layer; wherein the facestock layer has a first side and a second side; an adhesive layer comprising the composition of any of the preceding claims, after being cured, applied to at least a portion of the second side of the facestock layer.

9. The composition of claim 1, wherein the photoinitator is present in the composition at about 1.9% by weight percentage by weight of the composition.

10. A composition, comprising: a styrene-isoprene-styrene block copolymer; a polybutene polymer; a photoinitiator; and a tackifier.

11. The composition of claim 10, wherein the tackifier comprises cycloaliphatic hydrocarbon resins.

12. The composition, of claim 10 or 11, wherein: a percentage of the styrene-isoprene-styrene block copolymer is between about 15% and about 40% by weight; a percentage of the polybutene polymer is between about 15% and about 40% by weight; and a percentage of the tackifier is between about 30% and about 60% by weight.

13. A laminate, comprising: a facestock layer; wherein the facestock layer has a first side and a second side; an adhesive layer comprising the composition after being cured of claim 11 or claim 12 applied to at least a portion of the second side of the facestock layer.

14. The composition of any of claims 10-13, wherein the tackifier has a molecular weight average (M_w) between about 1600 g/mol and 2800 g/mol.

15. The composition of claim 10, the photoinitator is present in the composition at about 1.3% by weight percentage by weight of the composition.